Perfuming device for perfuming and sanitizing ambient air

ABSTRACT

The device is useful for the perfuming, deodorising or sanitising of ambient air or enclosed spaces and comprises a gel element resulting from the in situ cross-linking of a functionalised liquid polymer, or a copolymer with a cross-linking agent, in the presence of a perfume, deodorising or sanitising base.

TECHNICAL FIELD

The present invention relates to perfumery and more particularly itconcerns a perfuming device for purifying ambient air and enclosedspaces.

PRIOR ART

The utilisation of various devices for purifying ambient air hasmarkedly increased in recent years. Air-deodorisers, for example, havehenceforth become of current use in practically all households wherethey are used to mask bad odours as well as to impart ambientfragrances. The same applies to public places, e.g. offices or cars.

The solutions applied for the manufacture of this sort of devices areextremely varied. By way of example, one can mention here the systemsbased on the rapid diffusion of sanitising agents, which diffusion ispromoted by the action of dispersing devices of spray type, aerosol ormechanical. Also known are solid devices consisting of elementsimpregnated with active sanitising ingredients, which elements areconstituted by gels, such as agar-agar or sodium stearate gels, or bysynthetic resin or mineral material blocks, e.g. plaster or silica. Theprior art is also rich in examples wherein the deodorising devices areconstituted by plastic packing elements enclosing the active ingredientsin liquid form and wherein the diffusion of the sanitising vapours cantake place through polymer semi-permeable walls. Finally, well-known arealso the devices wherein the diffusion occurs by means of a wick putinto contact, at one of its ends, with a sanitising liquid.

By experience, it is apparent that none of the existing systems cansatisfy all the criteria of functionality and aesthetics required for ageneral use, some devices being more suitable for pulse perfuming ofsmall or large spaces, others, on the contrary, more adapted forcontinuous sanitization.

Amongst the simple systems of proved efficacy one can find those basedon the difflusion of sanitising agents wherein the support isconstituted by a gelified material. They are devices which use ingeneral the gelifying properties of carrageenans or alginates.

DESCRIPTION OF THE INVENTION

We have now discovered that it was possible to obtain gels, suitable asa support in deodorising or sanitising devices, by reacting, in thepresence of a perfuming base, a liquid polymeric material with across-linking agent.

As it will become more apparent at the reading of the specific examplesgiven hereinafter, the devices thus prepared offer several advantagesover the prior art devices. In this respect, one can mention the factthat the support, once shaped, appears as a rigid dry and transparentmaterial, which can contain a large proportion of perfume base, of up to90% or more. This last feature is particularly important since thedevices of the invention can accordingly be used in the form of discreetarticles of small dimension, notwithstanding of good effectiveness.Thus, for example, these devices can find a utilisation to perfumeclosed small spaces such as cars, bathrooms, lavatories and so on. Owingto their transparency, they can be shaped in various and aestheticallyappealing forms. What is more, their manufacture is very simple since,once homogenised, the polymer reaction mixture containing the perfumingbase occurs in the form of a liquid which can be easily poured intomoulds of the desired appropriate and varied form.

Lastly, solid articles can be shaped by reducing somewhat the proportionof the perfume base --e.g. to about 70% by weight relative to the weightof the polymer material --and by adding to the reaction mixture fillingagents such as plaster, sawdust, metal powder or other similarmaterials.

We have discovered that certain functionalised polymers could becross-linked in situ, in the presence of a perfume base, to form a gelwhich possessed the above-mentioned features.

The present invention provides a device for the perfuming, deodorisingor sanitising of ambient air or closed spaces, which device comprises agelified element resulting from the in situ cross-linking of a polymer,or a copolymer, in the presence of a perfuming, deodorising orsanitising base and/or a surfactant agent.

More particularly, the invention provides a device containing a gelifiedelement resulting from the in situ cross-linking of a functionalisedliquid polymer, or copolymer, and a cross-linking agent, in the presenceof a perfuming, deodorising or sanitising base and/or a surfactantagent.

The invention also has as an object a process for perfuming a surfactantagent, which process is characterised in that a polymer, or copolymer,is cross-linked in situ in the presence of an active surfactant and aperfume base.

Preferred functionalised polymers according to the invention include thepolymer materials miscible to the current perfume materials, whichpolymers possess one or several functional groups. Likewise, thecross-linking agent must possess one or more complementary functionalgroups. The mixture of these two elements gives, in the presence of aperfume base, a reaction which results in the formation of athree-dimensional network enclosing the perfume base.

The functional groups and the complementary functional groups may berespectively carboxylic acid, anhydride or acid chloride derived groupsand amine or alcohol groups. Preferably, one can choose liquid polymerspossessing functions derived from carboxylic acids, anhydrides or acidchloride and cross-linking agents having an amine or an alcohol fiction,but the reverse can also apply.

The functional groups on the polymer or the cross-linking agent may bemono-or poly-functional. To obtain a three-dimensional network, it ishowever necessary to have the presence of at least two functional groupsper molecule of the liquid polymer and of the cross-linking agent alike.

By the terms "functionalised liquid polymer" it is deemed here to referto a material which is liquid at room temperature and which possesses aviscosity of not more than 5000 poise at 25° C., preferably of about 250to 1000 poise. As indicated above, both the liquid polymer material andthe cross-linking agent must be soluble in the perfume base. Solubilitycan be achieved by straight solution in the perfume base or by adding anappropriate specific solvent. In practice, we have observed that byusing large proportions of perfume base, such as those employedaccording to a preferred embodiments of the invention, such acomplementary addition of solvent is not necessary.

The polymer material can be selected amongst the numerous polymerscapable of functionalization. Preferred polymers are selected from thegroup of polyolefines, more particularly amongst polymers derived frommono- or di-olefines containing, prior to functionalization, at leastone, and more preferably several, vinyl groups.

PREFERRED EMBODIMENTS OF THE INVENTION

According to a preferred embodiment of the invention, there are usedpolymers which are derivatives of butadiene, isoprene or chloroprene.More preferred is maleinised polybutadiene of MW 5000-20,000, ormaleinised polyisoprene of MW 200,000-500,000. These are commerciallyavailable materials. Examples of these materials are provided in EPpatent application N° 023 084, the disclosure of which is enclosedherein by reference. As an example, one can mention the product knownunder the name of "Lithene" origin: Revertex Ltd!. Amongst the differentqualities of available Lithene, good results have been obtained by using"Lithene N4-9000 10MA" origin: Revertex Ltd!; 9000 stands for themolecular weight of polybutadiene before maleinisation, whilst 10MAindicates the degree of maleinisation --in this case 10 parts of maleicanhydride per 100 parts of polybutadiene (=about 9.1%) --.

The above-cited EP patent application gives also indications concerningthe choice of cross-linking agents. The discriminating criterion forthis selection is represented by the solubility of such an agent in thereaction medium, namely in the components of the perfume base. Assuggested in the cited EP application, agents which satisfy such acriterion include dihydroxy polybutadiene. Ethoxylated primary aminesare however preferred. Amongst the latter, more preferred areoleylamines possessing 2 moieties of ethylene oxide per molecule. Othercross-linking agents can be selected amongst the group ofalkylpropyldiamines having an ethoxylated or propoxylated higheraliphatic chain (e.g. "Dicrodamet" ; origin: Croda Chemicals Ltd),diethanolamine or diethylenetriamine.

Equally useful have been found to be the cross-linking agentsconstituted by polyoxy- alkylenediamines. More particularly, the use ofJeffamine D-400, Jeffamine EDR-148 and Jeffamine D-2000 is veryadvantageous (Jeffamine is a registered trademark of Huntsman Corp.).

Also useful according to the invention are cocoamines having 5 ethyleneoxide units per molecule. These are commercial products known under thename of "Crodamet" origin: Croda Chemicals Ltd!.

The functionalised liquid polymer and the cross-linking agent are mixedin a molar ratio of between about 3:1 and 0.5:1, preferably of 1:1,based on the molar ratio of the functional groups which are present.

The gelified element according to the invention can also be obtained bymixing two polymers possessing complementary functionalities. Of course,the two polymers must be soluble in the perfuming or sanitising base.For example, it is possible to use a polybutadiene having a hydroxylicfunction such as HFPB (origin:Revertex Ltd) which gelifies when admixedwith maleinised polybutadiene. Sometimes, the use of specific catalystsallows better control of the gel formation and, to this end, there areused tertiary amines (e.g.: DAMA 1010 ; origin: Albemarle SA). Mixturesof Hycar CTBN 1300 ×21 (origin: B. F. Goodrich) and maleinisedpolybutadiene are also perfectly convenient.

According to a variant of the invention device, a copolymer is used aspolymer, instead of a functionalised liquid polymer. Suitable copolymersinclude EMA, a copolymer of ethylene and maleic anhydride, a freeflowing homogeneous powder.

As a perfume base there is used in the device of the invention any ofthe current compositions used in perfumery. These can be discreetchemicals; more often, however, they are more or less complex mixturesof volatile liquid ingredients of natural or synthetic origin. Thenature of these ingredients can be found in specialised books ofperfumery, e.g. in S. Arctander (Perfume and Flavor Chemicals, MontclairN.J., USA 1969).

As indicated above, one of the characterising elements of both thefunctionalised liquid polymer and the cross-linking agent, useful forthe preparation of the invention's device, is their solubility in theperfuming, deodorising or sanitising base chosen. It is also understoodthat both the liquid polymer and the cross-linking agent can bedissolved in appropriate organic solvents before cross-linking. However,such an operation is superfluous in most of the cases, the active base,especially the perfume base, being sufficient to dissolve them and theuse of a supplementary solvent being unnecessary.

Although special mention has been made hereinabove of the perfumingeffect exerted by the invention device, the same principles apply to themanufacture of analogous devices for the diffusion of deodorising orsanitising vapours, the perfume base being then replaced by adeodorising composition, a bactericide, an insecticide, a repellent oreven an attractant. By the term "sanitising", we refer here not only tothose substances which can enhance the degree of acceptance ofsurrounding air by the observer, but also to those substances which canexert an attractant or repellent effect towards certain species ofinsects, for instance towards houseflies or mosquitoes, or else asbactericide.

One of the objects of the invention is therefore to provide a perfuming,deodorising or sanitising device containing a gelified element resultingfrom the in situ cross-linking between a functionalised liquid polymer,or a copolymer, and a cross-linking agent, in the presence of aperfuming, a deodorising or a sanitising base.

The invention is better illustrated by the following examples whereinthe abbreviations have the meaning common in the art and thetemperatures are indicated in degrees centigrade.

EXAMPLE 1

2.23 g of Lithene N4-9000 10MA and 10.28 g of a perfume base (Splash115.032 BGE; origin: Firmenich SA, Geneva, Switzerland) were manuallymixed in an appropriate vessel. 0.34 g of Crodamet 02 were then addedunder stirring. After about 10 min at room temperature, the resultingpolymer oil gelled encapsulating the perfume base. Gel setting wascomplete in about half an hour.

EXAMPLE 2

2.56 g of Lithene N4-9000 10MA and 12.43 g of a perfume base (Splash115.032 BGE; origin: Firmenich SA, Geneva, Switzerland) were manuallymixed, whereupon 0.55 g of Crodamet C5 were added under stirring. Afterabout 2 hours at room temperature, the oil had gelled into a non-wettinglump. Even after 24 h the product was not as rigid as that prepared inExample 1.

EXAMPLE 3

2.29 g of Lithene N4-9000 10MA and 14.95 g of a perfume base (Splash115.032 BGE; origin: Firmenich SA, Geneva, Switzerland) were stirred byhand, whereupon 1.98 g of Crodamet 02 were added with stirring. Afterapproximately 20 min at room temperature, the oil mixture had gelled.The product was fully cured after approximately 50 min. The resultingproduct was softer than that prepared according to Example 2 whichcontained 80% by weight of the perfume base.

EXAMPLE 4

1.44 g of Lithene N4-9000 10MA were mixed by hand in a beaker with 14.93g of a perfume base (Splash 115.032 BGE; origin: Firmenich SA, Geneva,Switzerland), whereupon 0.22 g of Crodamet 02 were added under stirring.After 40 min, the mixture gels. The product was fully cured afterapproximately 3 h. The resulting product, which encapsulated 90% byweight of the perfume base, was softer than those obtained according toExamples 2 and 3, which contained 80 and 85% by weight of perfume base,respectively.

EXAMPLE 5

2.50 g of Lithene N4-9000 10MA were placed in a beaker and 11.60 g of aperfume base (Brissago 144.034; origin: Firmenich SA, Geneva,Switzerland) were added and stirred by hand, whereupon 0.4 g of Crodamet02 were added under manual stirring. The resulting oily mixture was thenpoured into Barex type moulds. After 15 min at room temperature, the oilhad gelled into a rubbery, non-wetting lump.

EXAMPLE 6-8

By proceeding as indicated in the previous example but replacing theperfume base Brissago with identical proportions of Centifoline 144.036,Citronia 144.037 and Tristan 431.756 (origin: Finnenich SA, Geneva,Switzerland) there were obtained perfuming gels of good quality with agelling time of between 10 and 25 min.

EXAMPLE 9

2.54 g of Lithene N4-9000 10MA and 6.23 g of a perfume base (Terminator109365B; origin: Firmenich SA, Geneva, Switzerland) were mixed by handand 0.13 g of Crodamet 02 (ratio: Lithene/Crodarnet ca. 3: 1) were addedthereto under stirring. The resulting oil gelled in 15 min at ambienttemperature.

EXAMPLE 10

By proceeding as indicated in the previous example but using a molarratio of Lithene/Crodamet of 5: 1 instead of 3: 1, there is obtained asticky gel which lacked a certain degree of rigidity.

EXAMPLE 11

1.87 g of Lithene N4-9000 10MA were mixed with 5.69 g of a perfume base(Terminator 109365B; origin: Firmenich SA, Geneva, Switzerland),whereupon 0.57 g of Crodamet 02 were added thereto under manualstirring. After approximately 20 min at room temperature, the oilgelled.

EXAMPLE 12

Approximately 2 g of Lithene N4-9000 10MA were placed in a beaker andmixed with the required amount of a perfume base (Honeysuckle 150061;origin: Firmenich SA, Geneva, Switzerland) until complete solution. Thecross-linking agents were pre-mixed and added under stirring to theperfume polymer base, then the mixture was poured into appropriatemoulds and left to rest at room temperature until complete gel setting.

    ______________________________________                                        % w/w Honeysuckle 150061                                                                       80.00   80.00   80.00 80.00                                  % w/w Lithene N4-9000 10M-A                                                                    17.14   17.49   17.85 18.24                                  % w/w Jeffamine D-400                                                                           2.86    2.27    1.66  1.01                                  % w/w Jeffamine EDR-148                                                                        --       0.24    0.49  0.75                                  Gelling time (min)                                                                             59      33      21    7                                      ______________________________________                                    

EXAMPLE 13

2.13 g of Lithene N4-9000 10MA were placed in a beaker and mixed with9.94 g of a perfume base (Beach 68536; origin: Firmenich SA, Geneva,Switzerland). After complete solution, 0.35g of Jeffamine D-400 wereadded under stirring. 5 g of the mixture (which corresponds to 4 g ofperfume base) were poured into a thermoformed pouch (28 ×46 mm) and letsetting at room temperature. Left in the air, the gel lost 86% of theoriginal weight of the perfume base in 43 days. Similar results wereobtained by using Fresh Bouquet 433213 as perfume base (origin:Firmenich SA) used in the gel at a concentration of 80% by weight.

EXAMPLE 14

1.55 g of Lithene N4-9000 10MA were poured into an appropriate containerand mixed with 3.82g of a perfume base (Lavande de Provence 150060(origin: Firmenich SA, Geneva, Switzerland) until complete solution. Ina separate beaker, 1.87 g of Hycar CTBN 1300 ×21 (origin: B.F. Goodrich)were dissolved in 4.13 g of the same perfume base, and 5.37 g of thissolution were added to the previously obtained perfumed solution of thepolymer. A dry and rigid gel formed rapidly at ambient temperature.

EXAMPLE 15

17.14 g of Lithene N4-9000 10MA were added to a mixture constituted by40 g of a liquid surfactant and 40 g of orange terpenes and the mixturewas stirred by hand until complete solution. 2.86 g of Jeffamine D-400were added thereto under stirring. In less than 2 minutes at ambienttemperature, the mass gelled.

The surfactant used was any of the following:

15.1 Marlipal 24/70*

15.2 Marlipal O13/70*

15.3 Lutensol ON70**

(*) origin: Huls

(**) origin: BASF

I claim:
 1. An anhydrous gel element comprising the cross-linkedreaction product ofa polymer selected from the group consisting of afunctionalized liquid polymer and a copolymer of ethylene and maleicanhydride, and a cross-linking agent having at least one complementaryfunctional group, in the presence of a perfume component comprising aperfume base, a deodorizing base, a sanitising base, or a surfactant,wherein the functionalized liquid polymer is maleinised polybutadiene ormaleinised polyisoprene, and the polymer is sufficiently cross-linked bythe cross-linking agent in the presence of the perfume component toencapsulate a portion of the perfume component.
 2. The anhydrous gelelement according to claim 1 wherein the polymer and the cross-linkingagent are soluble in the perfume component.
 3. The anhydrous gel elementaccording to claim 1 wherein the polymer is maleinised polybutadienehaving a molecular weight of 5,000 to 20,000 or maleinised polyisoprenehaving a molecular weight of 200,000 to 500,000.
 4. The anhydrous gelelement according to claim 1 wherein the cross-linking agent is selectedfrom the group consisting of dihydroxypolybutadiene, an ethoxylatedprimary amine, an alkylpropyldiamine having an ethoxylated higheraliphatic chain, an alkylpropyldiamine having a propoxylated higheraliphatic chain, diethanolamine, diethylenetriamine, apolyoxy-alkylenediamine, and a cocoamine having 5 ethylene oxide units.5. The anhydrous gel element according to claim 4 wherein theethoxylated primary amine is an oleylamine having 2 ethylene oxideunits.
 6. The anhydrous gel element according to claim 3 wherein thecross-linking agent is an oleylamine having two ethylene oxide units ora cocoamine having five ethylene oxide units per molecule.
 7. Theanhydrous gel element according to claim 3 wherein the polymer and thecross-linking agent are present in a molar proportion of about 1:1. 8.The anhydrous gel element according to claim 1 wherein the perfumecomponent is present in an amount of about 70% to 90% by weight based onthe weight of the polymer and the cross-linking agent.
 9. A devicecomprising the anhydrous gel element of claim
 1. 10. A method ofperfuming, deodorizing or sanitising air, which comprises exposing theair to the anhydrous gel element in the device of claim
 9. 11. Ananhydrous gel element comprising the cross-linked reaction product of ahydroxylic polybutadiene and a maleinised polybutadiene, in the presenceof a perfume component comprising a perfume base, a deodorizing base, asanitising base, or a surfactant, wherein the maleinised polymer issufficiently cross-linked to the hydroxylic polybutadiene in thepresence of the perfume component to encapsulate a portion of theperfume component.
 12. The anhydrous gel element of claim 11 furthercomprising a tertiary amine.
 13. A method of perfuming a surfactantmaterial, which comprises:providing a mixture of a surfactant, a perfumebase, a functionalized liquid polymer or a copolymer of ethylene andmaleic anhydride, and a cross-linking agent, wherein the functionalizedliquid polymer is selected from the group consisting of maleinisedpolybutadiene and maleinised polyisoprene, and the cross-linking agenthas at least one complementary functional group; and cross-linking thepolymer in the presence of the surfactant and the perfume base toproduce an anhydrous gel element.